The present invention relates to a polyolefin composition in powder form comprising (i) a crosslinkable, vinyl silane-grafted blend of a olefinic interpolymer, optionally containing a crystalline polypropylene homopolymer or interpolymer; and (ii) a crosslinked vinyl silane-grafted olefinic interpolymer containing a cure or crosslinking catalyst; the above blend optionally containing a crystalline polyolefin powder. In another aspect, this invention relates to a process for preparing these polyolefin powders, and applications for using these powders. In a further aspect, this invention relates to laminates, both foamed and unfoamed, prepared from these polyolefin powders. In yet another aspect, this invention relates to processes to prepare these laminates.
Automotive interior coatings are produced by a variety of techniques including vacuum molding and thermoforming of calendered or extruded sheets. If the mold has sharp corners or deep draw regions, then the molding process can lead to thinning of the material in these areas and significant loss of grain texture. Vacuum formed sheets, after cooling, can also contain a high residual molding stress caused during the molding process which, when reheated in subsequent back-foaming steps, can result in release of this stress. This, in turn, can cause shrinkage and dimensional stability problems. These stress areas can also lead to cracks forming over time as the skin ages.
An alternative process which is less susceptible to these problems is slush molding. In the slush molding technique, a free-flowing, powdered polymer is charged to an open top container or box, i.e., a slush box. A heated mold in the form of the article or object to be molded is clamped on top of the slush box, and the container rotated in a manner such that the free-flowing polymer powder contacts the hot mold where the powder melts and flows over the mold. The container is then returned to its original position, the mold removed from the container, and the article removed from the mold. This technique can realize complex shapes with sharp edges and excellent grain retention.
Introduction of passenger and door airbags has changed the requirement for automotive interior coverings from predominately appearance only criteria to that of a safety composition. Until recently, polyvinyl chloride (PVC) resins were the material of choice for interior coverings, and they are ideally suited for slush molding. However, PVC formulations suffer from migration and volatilization of the plasticizers over time, and this leads both to physical property changes in the PVC as it ages and to fogging of the car window glass. PVC also suffers from being heavier than alternative polyolefin materials (an important consideration in the current design of automobiles with the emphasis on lighter materials to reduce the overall weight of the vehicle and thus increase its gas efficiency). Additionally, the hardness, storage modulus, and brittleness of PVC increases as the ambient temperature decreases, and thus at low temperatures, e.g., about minus 40xc2x0 C., the instrument panel skin upon airbag deployment could splinter.
An alternative to PVC is thermoplastic polyurethanes (TPU) which can be engineered to have the necessary flow characteristics required for slush molding. Such TPUs have good scratch and mar properties but the aromatic based TPUs have poor ultraviolet (UV) light resistance. Aliphatic isocyanates can be used to prepare TPUs having good UV-resistance but at a significant cost penalty.
Another problem with many existing compositions used in the slush molding process is poor hot tear resistance which can sometimes cause tearing of the molded product if it is removed from the mold while still hot. Having to wait for the molded article to cool increases production time and reduces efficiency.
Thus, there is a need by the automobile manufacturers and others to develop a polymer composition for automotive interior applications, especially polymer powder for slush molding operations, which has good hot tear properties, excellent low temperature properties, low hardness and no glossing after heat aging.
One embodiment of this invention is a polyolefin powder comprising about 80 to 95 wt % of component A, about 5 to 10 wt % of component B, and, optionally, 0 to 10 wt % of component C. Component A comprises a first powder of about 60 to about 99.9 wt % of a crosslinkable, silane-grafted, olefinic interpolymer, and, optionally, about 0.1 to about 40 wt % of a crosslinkable, silane-grafted, crystalline polypropylene homopolymer or interpolymer. Component B comprises a second powder of about 98 to 99.9 wt % of a crosslinked, silane-grafted, olefinic interpolymer, and from about 0.1 to 2 wt % of a cure catalyst. Component C comprises a crystalline polyolefin powder having a particle size of not greater than 500 microns. Optionally, the polyolefin powder blend of A, B, and C contains a blowing agent, typically a chemical blowing agent. Components A and B are prepared independently and blended together, optionally with Component C, to prepare the polyolefin powders of this invention. If Component C is absent from the polyolefin blend powder of the invention, then Component A comprises a polypropylene homopolymer or interpolymer.
In another embodiment of the invention, a process for preparing a polyolefin powder comprises the steps of:
(A) Contacting under grafting conditions (i) at least one olefinic interpolymer (ii) an unsaturated silane compound, and (iii) a free radical generating compound, to form a first silane-grafted, olefinic interpolymer;
(B) Melt blending from about 60 to about 99.9 wt % of the first silane-grafted, olefinic interpolymer with about 0.1 to about 40 wt % of at least one crosslinkable, silane-grafted, crystalline polypropylene homopolymer or interpolymer to form a first polymer blend;
(C) Forming the first polymer blend into a first powder;
(D) Mixing under grafting conditions (i) an olefinic interpolymer (ii) an unsaturated silane compound, and (iii) a free radical generating compound, to form a second silane-grafted, olefinic interpolymer,
(E) Curing the second silane-grafted olefinic interpolymer to a gel content of at least 10%;
(F) Forming the second silane-grafted, olefinic interpolymer into a second powder; and
(G) Mixing the first and second powders to form a polyolefin powder comprising about 90 to 95 wt % of the first powder and about 5 to 10 wt % of the second powder.
Certain of the steps of the process can be practiced in any order, e.g., steps D-F can precede or be performed simultaneously with steps A-C. In addition, step (G) can further comprise mixing the first and second powders with about 0.1 to about 10, preferably about 1 to about 8 and more preferably about 2 to about 7, wt % of a crystalline polyolefin powder having a particle size of not greater than about 500 microns.
In another embodiment of the invention, a process for preparing a polyolefin powder comprises the steps of:
(A) Melt blending from about 60 to about 99.9 wt % of at least one olefinic interpolymer with about 0.1 to about 40 wt % of at least one crystalline polypropylene homopolymer or interpolymer into a olefinic interpolymer blend;
(B) Contacting under grafting conditions (i) an olefinic interpolymer blend from step (A) (ii) an unsaturated silane compound, and (iii) a free radical generating compound, to form a first silane-grafted, olefinic interpolymer blend;
(C) Forming the first silane-grafted olefinic interpolymer blend into a first powder;
(D) Mixing under grafting conditions (i) at least one olefinic interpolymer (ii) an unsaturated silane compound, and (iii) a free radical generating compound, to form a second silane-grafted, olefinic interpolymer,
(E) Curing the second silane-grafted olefinic interpolymer to a gel content of at least 10%;
(F) Forming the second silane-grafted, olefinic interpolymer into a second powder; and
(G) Mixing the first and second powders to form a polyolefin powder comprising about 90 to 95 wt % of the first powder and about 5 to 10 wt % of the second powder.
Certain of the steps of the process can be practiced in any order, e.g., steps D-F can precede or be performed simultaneously with steps A-C. In addition, step (G) can further comprise mixing the first and second powders with about 0.1 to about 10, preferably about 1 to about 8 and more preferably about 2 to about 7, wt % of a crystalline polyolefin powder having a particle size of not greater than about 500 microns.
In yet another embodiment the invention is a process for preparing a polyolefin powder, the process comprising the steps of:
(A) Blending under grafting conditions (i) an olefinic interpolymer (ii) an unsaturated silane compound, and (iii) a free radical generating compound, to form a first silane-grafted, olefinic interpolymer;
(B) Forming the first silane-grafted, olefinic interpolymer into a first powder;
(C) Blending under grafting conditions (i) an olefinic interpolymer (ii) an unsaturated silane compound, and (iii) a free radical generating compound, to form a second silane-grafted, olefinic interpolymer,
(D) Curing the second silane-grafted olefinic interpolymer to a gel content of at least 10%;
(E) Forming the second silane-grafted, olefinic interpolymer into a second powder; and
(F) Forming a polyolefin powder from the first and second powders and a crystalline polyolefin powder having a particle size of not greater than about 500 microns, such that the blend composition comprises about 80 to 95 wt % of the first powder, about 5 to 10 wt % of the second powder, and about 0.1 to about 10, preferably about 1 to about 8 and more preferably about 2 to about 7, wt % of the crystalline polyolefin powder.
Here too, the order of the various steps can be changed, e.g., steps C-E can precede or be performed simultaneously with steps A-B. Moreover, step A can further comprise mixing about 60 to about 99.9 wt % of the first silane-grafted, olefinic interpolymer with about 0.1 to about 40 wt % of at least one crosslinkable, silane-grafted, crystalline polypropylene homopolymer or interpolymer to form a polymer blend from which the first powder is formed.
The compositions of this invention are especially useful in slush molding applications where polymers need to have good melt flow to allow for a uniform and fast distribution of the polymer in the mold. This is a surprising result since Component B of the invention exhibits little, preferably no flow at 190xc2x0 C. when tested for melt index (MI) according to ASTM D-1238 condition E. Additionally surprising is the crosslinked polyolefin of Component B is still able to release the cure catalyst and achieve uniform cure of the slush molded article. Furthermore, slush molded articles prepared from compositions of this invention usually exhibit one or more of low hardness, excellent grain retention, no glossing after aging at 120xc2x0 C., good scratch and mar resistance, excellent tensile and tear strength, a substantial absence of pinholes, and recyclability.
The use of a crosslinked catalyst carrier (Component B) has several advantages over existing methods of adding the cure catalyst. One advantage is the ability to prepare a complete slush molding formulation which has excellent stability against premature crosslinking. Typically, existing formulators add the neat cure catalyst as the last ingredient of a slush molding formulation just before molding to minimize premature crosslinking.
The polyolefin powders of this invention can also be used to perform xe2x80x9cdouble slushxe2x80x9d operations to prepare laminates. Specifically, after forming the first polymer layer or skin by slush molding, a second powder formulation containing a chemical blowing agent is molded onto the backside of the first polymer skin layer while the first skin layer is still in the mold. Heating the mold containing the first skin and the sintered foam formulation of this invention leads to foaming of the second slush layer and the formation of an in situ foam laminate with excellent adhesion between the first skin and the foam layer. No priming of the skin is needed, and this technique brings skin manufacturers closer to the goal of automotive interior laminates and coatings made entirely of polyolefinic materials (which are easier to recycle than laminates and coatings made of different polymeric materials). The crosslinked foam resists deformation at elevated temperature and are very soft and result in laminates with excellent haptics.
In addition to slush molding, powder compositions of this invention are useful in other molding methods including flow dipping, electrostatic coating, flame spray coating, and rotational molding.
Olefinic interpolymers useful in preparing Component A of this invention include ethylene/xcex1-olefin interpolymers having a density of less than 0.91 g/cm3, the interpolymer preferably having a weight ratio of ethylene to xcex1-olefin of about 90:10 to 30:70, more preferably about 85:15 to 40:60, the xcex1-olefin preferably a C3-C20 linear, branched or cyclic xcex1-olefin, the interpolymer preferably having a Shore A hardness of 95 or less. The term interpolymer refers to a polymer made from at least two monomers. It includes, for example, copolymers, terpolymers and tetrapolymers. Examples of C3-C20 xcex1-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. The xcex1-olefin can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an xcex1-olefin such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. Although not xcex1-olefins in the classical sense of the term, for purposes of this invention certain cyclic olefins, such as norbornene and related olefins, are xcex1-olefins and can be used in place of some or all of the xcex1-olefins described above. Similarly, styrene and its related olefins (for example, xcex1-methylstyrene, etc.), vinyl acetates, acrylates, and methacrylates are xcex1-olefins for purposes of this invention. Illustrative copolymers include ethylene/propylene, ethylene/butene, and ethylene/1-octene. Illustrative terpolymers include ethylene/propylene/1-octene, ethylene/propylene/butene, ethylene/butene/1-octene, and ethylene/butene/styrene.
More specific examples of olefinic interpolymers useful in this invention include ultra low density polyethylene (ULDPE) (e.g., Attane(copyright) ethylene/1-octene polyethylene made by The Dow Chemical Company), homogeneously branched, linear ethylene/xcex1-olefin copolymers (e.g. Tafmer(copyright) by Mitsui Petrochemicals Company Limited and Exact(copyright) by Exxon Chemical Company), homogeneously branched, substantially linear ethylene/xcex1-olefin polymers (e.g. Affinity(copyright) polymers available from The Dow Chemical Company and Engage(copyright) polymers available from DuPont Dow Elastomers L.L.C.), and high pressure, free radical polymerized ethylene copolymers such as ethylene/vinyl acetate (EVA) polymers (e.g., Elvax(copyright) polymers manufactured by E. I. Du Pont du Nemours and Co.), and ethylene/acrylate polymers (e.g., Elvaloy(copyright) polymers manufactured by E. I. Du Pont du Nemours and Co.). The more preferred olefinic polymers are the homogeneously branched linear and substantially linear ethylene copolymers with a density (measured in accordance with ASTM D-792) from about 0.85 to less than 0.91 g/cm3, especially from about 0.85 to about 0.90 g/cm3, and a melt index (measured in accordance with ASTM D-1238 (190C/2.16) of about 10-500, preferably 15-150 g/10 minutes. The substantially linear ethylene copolymers are especially preferred, and are more fully described in U.S. Pat. No. 5,986,028 which is incorporated herein by reference. Blends of any of the above olefinic interpolymers can also be used in this invention.
Suitable crystalline polypropylene homopolymers or interpolymers optionally used in the preparation of Component A include polypropylene homopolymers, polypropylene interpolymers including interpolymers of propylene with at least one C4-C20 xcex1-olefin such as 1-butene, 1-hexene or 4-methyl-1-pentene, copolymers of propylene and ethylene, and blends of any of the above crystalline polypropylenes, the interpolymer preferably having a weight ratio of propylene to xcex1-olefin of about 98:2 to 70:30, more preferably about 95:5 to 80:20. As here used and also as used in the description of Component C, xe2x80x9ccrystallinexe2x80x9d means a crystallinity of greater than about 30 percent. The polypropylene homopolymers are generally in the isotactic form although other forms of polypropylene can be used (e.g., syndiotactic or atactic). Preferred crystalline polyolefins include polypropylene homopolymers and copolymers of polypropylene which are comprised of at least about 50% propylene by weight. The copolymer may be a random copolymer or a block copolymer or a blend of a random copolymer and a block copolymer. The polypropylene homopolymer or copolymer has a melt flow ration (MFR) (230xc2x0 C. and 2.16 kg weight) of at least 0.1 g/10 min, preferably greater than 5 g/10 min. Other suitable crystalline polypropylenes include branched polypropylene homopolymers and branched copolymers of polypropylene. Examples of preferred crystalline polypropylene polymers include Inspire(copyright) polymers (available from The Dow Chemical Company). For applications needing improved tear properties, preferably the crystalline polypropylene is blended with the olefinic interpolymer of this invention.
Suitable crystalline polyolefin powders useful as Component C include polyethylene homopolymers, linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), or interpolymers of ethylene with at least one xcex1-olefin of from 3 to 20 carbon atoms such as 1-propylene, 1-butene, 1-isobutylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. Preferably, when HDPE is an interpolymer, it is a copolymer of ethylene and 1-octene. However, most preferably the HDPE is an ethylene homopolymer. Preferably Component C is a crystalline polyolefin having greater than 50 wt % ethylene and having a melting point greater than 90xc2x0 C., preferably above 100xc2x0 C., more preferably above 110xc2x0 C., and most preferably above 120xc2x0 C. The density of suitable ethylene homopolymers or interpolymers (as measured in accordance with ASTM D-792) is generally at least about 0.90, preferably at least about 0.92 and more preferably at least about 0.93 g/cc. The maximum density is typically not greater than about 0.96 g/cc. Generally, the melt index (MI) of suitable ethylene homopolymers or interpolymers useful for Component C (as measured according to ASTM D-1238 condition E) is of about 10-500, preferably of about 10-250, and more preferably of about 10-100 g/10 min. Examples of suitable crystalline polyethylene polymers for Component C of this invention include Coathylene(trademark) polymers (available from E. I. DuPont de Nemours and Company). Blends of any of the above polymers can also be used in the practice of this invention for the preparation of Component C.
Additionally, the particle size of Component C is important in obtaining reduced pinhole formation and tear properties in articles made from the polyolefin powders of this invention. If the particle size is too large, the components do not mix uniformly, and this produces poor physical properties relative to polyolefin powders that are substantially uniformly mixed. The preferred particle size for Component C is less than 500, more preferably less than 350 and most preferably less than 250, microns (xcexcm).
The crystalline polyolefin used in Components A and C can also be a blend of crystalline polyolefins or a blend of at least one crystalline polyolefin with one or more other thermoplastics. Such blends can be prepared in situ (e.g., by having a mixture of catalysts in a single polymerization reactor or by using different catalysts in separate reactors connected in parallel or in series) or by physical blending of polymers such as by known melt or dry blending techniques. If a mixture, then the mixture contains at least about 70, preferably at least about 80 and more preferably at least about 90, weight percent of at least one crystalline polyolefin.
The vinyl silane grafted, or simply silane-grafted, olefinic interpolymers useful in preparing Components A and B of this invention are prepared by grafting a vinyl silane onto the olefinic interpolymer and the crystalline polypropylene homopolymer or interpolymer. Any silane, or a mixture of such silanes, that will effectively graft to the interpolymer can be used in the practice of this invention. Suitable silanes include those of the general formula: 
in which Rxe2x80x2 is a hydrogen atom or methyl group; x and y are 0 or 1 with the proviso that when x is 1, y is 1; n is an integer from 1 to 12 inclusive, preferably 1 to 4; and each R independently is a hydrolysable organic group such as an alkoxy group having from 1 to 12 carbon atoms-(e.g. methoxy, ethoxy, butoxy), aryloxy group (e.g. phenoxy), aralkoxy group (e.g. benzyloxy), aliphatic acyloxy group having from 1 to 12 carbon atoms (e.g. formyloxy, acetyloxy, propanoyloxy), amino or substituted amino groups (alkylamine, arylamino), or a lower alkyl group having 1 to 6 carbon atoms inclusive, with the proviso that not more than two of the three R groups is an alkyl (e.g., vinyl dimethyl methoxy silane). Silanes useful in curing silicones which have ketoximino hydrolysable groups, such as vinyl tris(methylethylketoamino) silane, are also suitable. Useful silanes include unsaturated silanes that comprise an ethylenically unsaturated hydrocarboxyl group, such as a vinyl, ally, isopropyl, butyl, cyclohexenyl or gamma-(meth)acryloxy allyl group, and a hydrolysable group, such as, for example, a hydrocarbyloxy, hydrocarbonyloxy, or hydrocarbylamino group. Examples of hydrolysable groups include methoxy, ethoxy, formyloxy, acetoxy, proprionyloxy, and alkyl or arylamino group. Preferred silanes are the unsaturated alkoxy silanes which can be grafted onto the polymer. These silanes and their method of preparation are more fully described in U.S. Pat. No. 5,266,627 to Meverden, et al. Vinyl trimethoxy silane, vinyl triethoxy silane, gamma-(meth)acryloxy propyl trimethoxy silane and mixtures of these silanes are the preferred silanes for use in establishing crosslinks.
The amount of silane used in the practice of this invention can vary widely depending upon the nature of the interpolymer, the silane, the processing conditions, the grafting efficiency, the ultimate application, and similar factors, but typically at least 0.2, preferably at least 0.5, more preferably at least 0.7 wt % silane, is used when grafting onto the olefinic interpolymer(s) used to prepare Component A. When grafting silane functionality onto the olefinic interpolymer(s) used to prepare Component B, the amount of silane needed is typically at least 0.15, preferably at least 0.2, more preferably at least 0.25 wt %. Considerations of convenience and economy are usually the two principal limitations on the maximum amount of silane used in the practice of this invention, and typically the maximum amount of silane does not exceed 3.5, preferably it does not exceed 2.5, more preferably it does not exceed 2.0 wt %. Weight percent silane is the amount of silane by weight contained in the mixture of the interpolymer(s) plus any other polymer(s) included with the elastomer during grafting such as a crystalline polyolefin. An amount of less than 0.1 wt % is undesirable because it does not result in sufficient crosslinking to permit the polymer from resisting deformation at elevated temperatures. An amount in excess of 3.5 wt % is undesirable because it does not contribute to the mechanical integrity of the cured polymer and increases the cost of the formulation. Overcured systems can be detrimental to elongation at break properties. An indication of level of crosslinking may be determined from gel content of the elastomer.
The silane is grafted to the resin (interpolymer plus any other polymer(s) included with the interpolymer during grafting), by any conventional method, typically in the presence of a free radical initiator e.g. peroxides and azo compounds, or by ionizing radiation, etc. Organic initiators are preferred, such as any one of the peroxide initiators, for example, dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane, lauryl peroxide, and t-butyl peracetate. A suitable azo compound is azobis isobutyronitrile.
The amount of initiator can vary, but it is typically present in an amount of at least 0.04, preferably at least 0.06 wt %. Typically the initiator does not exceed 0.15, preferably it does not exceed about 0.10 wt %. The ratio of silane to initiator can also vary widely, but a typical silane:initiator ratio is about 10:1 to 30:1, preferably about 18:1 to 24:1.
While any conventional method can be used to graft the silane to the resin, one preferred method is blending the two with the initiator in the first stage of a reactor extruder, such as a single screw or a twin screw extruder, preferably one with a length/diameter (L/D) ratio of 20:1 or greater. The grafting conditions can vary, but the melt temperatures are typically between 160xc2x0 C. and 280xc2x0 C., preferably between 190xc2x0 C. and 250xc2x0 C., depending upon the residence time and the half life of the initiator.
The crosslinked vinyl silane grafted interpolymers used in component B of this invention are those described for component A except they must be crosslinked to a gel content (insoluble fraction) of at least 10% as determined by ASTM D 2765 using hot xylene as the solvent before blending with Component A. The interpolymer used in component B can be the same or different from the interpolymer used in component A and it can have the same or different levels of silane grafting as the interpolymers used in component A.
xe2x80x9cCrosslinkedxe2x80x9d, xe2x80x9csubstantially crosslinkedxe2x80x9d and similar terms mean that the polymer, in powder form or shaped into an article, has xylene extractables of less than or equal to 90 weight percent (i.e., greater than or equal to 10 weight percent gel content).
xe2x80x9cCuredxe2x80x9d means that the polymer, in powder form or shaped into an article, was subjected and exposed to a treatment which induced crosslinking.
xe2x80x9cCrosslinkablexe2x80x9d means that the polymer, in powder form or shaped into an article, is not cured or crosslinked and has not been subjected or exposed to treatment that has induced substantial crosslinking (although the polymer, in powder form or shaped into an article, comprises additive(s) or functionality which will effectuate substantial crosslinking upon subjection or exposure to such treatment (e.g., exposure to water).
Curing or crosslinking of the silane-grafted interpolymers of this invention is accelerated with a cure catalyst, and any catalyst that will provide this function can be used in this invention. These catalysts generally include organic bases, carboxylic acids and organometallic compounds including organic titanates and complexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin. Illustrative catalysts include dibutyl tin dilaurate, dioctyl tin maleate, dibutyl tin diacetate, dibutyl tin dioctoate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate and cobalt naphthenate. Tin carboxylates such as dibutyl tin dilaurate, dimethyl hydroxy tin oleate, dioctyl tin maleate, di-n-butyl tin maleate and titanium compounds such as titanium 2-ethylhexoxide are particularly effective for this invention.
The amount of catalyst, or mixture of catalysts, present in Component B is a catalytic amount, typically between about 0.1 to about 2 wt %, preferably between about 0.15 and 1.5 wt %, more preferably between about 0.25 and 1 wt %. The catalyst(s) serves a dual purpose. First, the catalyst accelerates the curing of Component B to a gel content of at least about 10 wt %. Second and after the cured Component B is mixed with Component A, the catalyst (still present in Component B) accelerates the curing of Component A.
The polyolefin powders of this invention can be used to make polyolefin laminates using a xe2x80x9cdouble slushxe2x80x9d process. The double slush process and apparatus for practicing the process are generally described in U.S. Pat. No. 4,664,864 and in Bouwman et al.: xe2x80x9cDouble Slushxe2x80x9d, Kunstoffe plast europe, vol. 90 part 3 (2000). Briefly stated and as it specifically relates to manufacture of a skin-foam laminate for automotive interior applications using the polyolefin powders of this invention, the double slush process comprises first heating a shell forming mold to about 280xc2x0 C. Next, into the open top of a slush box is added a polyolefin powder of the invention, and the heated mold is fixed to the top of the slush box. The slush box is then rotated through 360 degrees two and a half times and maintained in this position (upside down) for 10 seconds and then returned to the original position. Alternately, the box can be turned upside down to dump unfused powder out of the box for recovery. This forms the first skin layer that is typically about 0.1 to 1.0 mm in thickness on the shape-giving surface of the shell mold cavity.
The slush box is refilled with the composition of this invention containing 1 to 10 parts of a blowing agent such as azodicarbonamide. The slush box is then rotated through 360 degrees two and a half times and maintained in this position (upside down) for 10 seconds and then returned to the original position. The shell-forming mold is then heated to about 220xc2x0 C. for about ten minutes to expand the composition containing the blowing agent to fuse it with the skin. This forms a 1 mm skin layer with a foam backing typically of about 3 mm.
A major advantage of the polyolefin powders of this invention when used in a double slush operation is that both a skin layer and a foam layer can be made that have excellent compatibility with and adhesion to each other. No priming of the skin is needed.
Because of the variability in metal composition and surface treatment of molds used in slush molding operations, the demolding of the powder slush molded product prepared by the powders of this invention may require the use of a demolding additive to reduce adhesion of the molded article to the mold surface. Accordingly, it is often desirable before molding to coat the mold surface with a mold release agent such as dimethylpolysiloxane. For a continuous production of many moldings, however, the mold release agent is preferably added after only a few moldings, which leads to increased costs. Adding about 1 wt % or less of a methylpolysiloxane compound as an internally added mold release agent to the polyolefin powder (A plus B and C if present) is effective. The addition may be made either before or after the powdering.
The polyolefin powders of the present invention may additionally incorporate additives such as, slip and/or softening agents, oil extenders, scorch and/or cure retarders, heat and/or weather resistant stabilizers such as phenol-, sulfite-, phenylalkane-, phosphite-, amine- or amide-type stabilizers; antioxidants; antistatic agents; metal soaps; inorganic fillers; lubricants such as waxes; and pigments for coloration can be formulated in such an amount not to damage the object of the present invention.
Illustrative examples of slip agents include fatty acid, fatty acid amide, fatty acid ester, glycerin and wax. Examples of inorganic fillers include, calcium carbonate, calcium silicate, carbon black, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass balloon, basic magnesium sulfate whisker, calcium titanate whisker and aluminum borate whisker. One example of a scorch retarder is bis triethoxy silyl ethane.
The molded articles according to the present invention are useful products in the following various fields: (i) in the automobile fields, for example, various automobile parts including interior cover materials of, for example, instrument panels, console boxes, arm rests, head rests, door trims, rear panels, pillar trims, sunvisors, trunk room trims, trunk lid trims, air bag covers, seat buckles, head liners, gloves boxes and steering wheel covers; interior molded articles of, for example, kicking plates and change lever boots; exterior parts of, for example, spoilers, side moles, number plate housings, mirror housings, air dam skirt and mud guards; and other molded articles of automobile parts; (ii) in the sport good fields, decorative parts of sport shoes, grips of rackets, sport tools and goods of various ball games, covering materials of saddles and handlebar grips of bicycles, motor-cycles and tricycles, etc.; (iii) in the housing and building fields, covering materials of furniture, desks, chairs, etc.; covering materials of gates, doors, fences, etc.; wall decorative materials; covering materials of curtain walls; indoor flooring materials of kitchens, wash rooms, toilets, etc; outdoor flooring materials such as verandas, terraces, balconies, carports, etc.; carpets such as front door or entrance mats, table cloths, coasters, ash tray doilys; (iv) in the industrial part field, grips and hoses for electric tools, etc., and the covering materials thereof; packing materials; and (v) in other fields, covering materials of bags, briefcases, cases, files, pocket books, albums, stationary, camera bodies, dolls and the other toys, and molded articles such as watch bands, outer frames of picture or photograph and their covering materials.
Percent gel is determined according to ASTM D2765-95. Melt Index (I2) is determined at 190xc2x0 C. according to ASTM 1238/E and for I10 an ISO 1133/F standard is used. Tensile Strength and Elongation at break are determined using ISO 37 T2, Dumbell type 2 at a Test speed of 500 mm/min. Tear Strength is determined according to ISO 34C, Die C nicked sample. Particle size is determined by ASTM D 1921-96 Method B. Sixty degree gloss is determined by DIN 67530.
Molecular weight (MW) is determined by gel permeation chromatography (GPC) using a Waters 150C instrument. The pump was run at 55xc2x0 C. with the columns and detector run at 140xc2x0 C. The columns are #X mixed bed 10 um pl-gel. Injection volume is 200 xcexcl of a 0.14 wt % trichlorobenzene solution.
Pinholes are determined by visual inspection with the unaided eye of a 5 cm by 5 cm area of the material.